CN101632842B - Modification method used for surface of magnesium alloy stent - Google Patents
Modification method used for surface of magnesium alloy stent Download PDFInfo
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- CN101632842B CN101632842B CN2009100419777A CN200910041977A CN101632842B CN 101632842 B CN101632842 B CN 101632842B CN 2009100419777 A CN2009100419777 A CN 2009100419777A CN 200910041977 A CN200910041977 A CN 200910041977A CN 101632842 B CN101632842 B CN 101632842B
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Abstract
The invention discloses a modification method used for the surface of a magnesium alloy stent and contains controlledly degradable magnesium alloy stent surface micro-arc oxidation modification treatment and drug molecule biomimetic deposition; the magnesium alloy stent surface micro-arc oxidation modification treatment is first performed on the surface of magnesium alloy stent substrate to form controlledly degradable microporous ceramic oxide film with high porosity, the thickness of the film is 80-120mu m, the porosity is 20-40%; then drug molecule biomimetic deposition capable of promoting endothelial growth or dissolving thrombus and anticoagulating is performed on the microporous ceramic oxide film and the width of the settled layer is 5-10mu m. The modification of the surface of the magnesium alloy stent of the invention can effectively improve the in vivo biodegradation rate of the stent and the corresponding consistency of the mechanical property thereof, increase the compatibility between the stent and vascular walls, reduce the restenosis rate of blood vessels, lower the incidence of complications of patients and improve the survival rate and the life quality.
Description
Technical field
The present invention relates to alloy surface and change surname, be specifically related to the surface of magnesium alloy stent modification, belong to technical field of medical instruments.
Background technology
" the global disease burden in 2004 " of World Health Organization's issue shows; Cardiovascular disease is the main cause of death in the whole world; The global patient who dies from ischemic heart desease had 7,200,000 approximately in 2004, accounted for 12.2% of general mortality rate, in 20 common mortality rate diseases, was in first.Ministry of Health of China is analyzed Chinese city resident principal disease mortality rate in 2007 and is constituted and show that the heart disease mortality rate is 16.29% in " Chinese health statistics yearbook in 2008 ", only arrange after malignant tumor and cerebrovascular disease the 3rd.Cardiovascular death rate and disability rate are higher mainly contains ischemic heart desease and arteria coronaria thromboembolism; Cardiovascular disease needs daily life customs such as good diet, motion to go prevention, but the patient of ischemic heart desease, arteria coronaria thromboembolism etc. then needs cardiovascular surgery or support intervene operation to treat timely.
The interventional therapy that operation on vessels of heart is implanted with endovascular stent is main.Stent is on percutaneous puncture transluminal coronary angioplasty art basis, through conduit support is delivered to lesions, and makes its expansion back play the mechanics supporting role to blood vessel.Endovascular stent can prevent postoperative acute obturation effectively, and has reduced the incidence rate of restenosis.In the current extensive use clinically, some drawbacks of endovascular stent display, and form thrombosis in the support and cause vascular restenosis, and the material biocompatibility is bad etc.After endovascular stent is inserted in the body, with blood vessel wall to contact coupling with blood flow or the like problem particularly important, have only and improve the compatibility of support for blood vessel wall, blood, could reduce blood and deposit vascular restenosis phenomenon to cause at the thrombosis of rack surface.
Magnesium alloy has good bio-compatible degradability and certain Metal Mechanic Property; Chinese invention patent 200610109421.3 disclosed magnesium alloy blood vessel inner brackets can be accomplished in the interior degraded of interior back 6-18 week of implant into body body; Yet because the losing of constituent, and have influence on its most important, as to support mediation narrow blood vessel effect at the degradation process medium-height trestle.
Chinese invention patent application 200710012808.1 discloses a kind of medicine slow-release magnesium alloy bracket and application of degraded and absorbed fully; What the medication coat of endovascular stent adopted is high molecular degradable medicine painting method; But the combination of medicine and matrix can not combine effectively closely; When medicine 30 days slow release after the cycle magnesium alloy bracket matrix also accelerate degraded thereupon, and narrow blood vessel possibly come back to the pathological changes blocked state.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of safety and effectiveness and the method for modifying that is used for surface of magnesium alloy stent that slows down even eliminate the generation of vascular restenosis that strengthens magnesium alloy blood vessel inner bracket is provided.
The object of the invention is realized through following technical scheme:
A kind of method of modifying that is used for surface of magnesium alloy stent; The modification processing of surface of magnesium alloy stent differential arc oxidation and the bionical deposition of drug molecule that comprise controlled degradation; The magnesium alloy blood vessel inner bracket matrix surface carries out the magnesium alloy differential arc oxidation modification earlier to be handled; Form micropore ceramics oxidation film layer controlled degradation, that have fine and close porosity, thicknesses of layers 80-120 μ m, porosity 20-40%; On the micropore ceramics oxidation film layer, carry out urging the bionical deposition of drug molecule of endothelial growth or thrombolytic-anticoagulant, deposit thickness is 5-10 μ m;
It is after magnesium alloy bracket is taken out drying, to be 350-400W at output power of high-frequency switching power supply that described magnesium alloy differential arc oxidation modification is handled, and power density is 160-200W/cm
2, switching frequency is under the 180-250kHz condition, successively the phosphate electrolyte of 45-60 ℃ calcium salt electrolyte and 50-60 ℃ carry out respectively 20-30 minute with 15-20 minute differential arc oxidation, make rack surface obtain the micropore ceramics oxidation film layer; Said calcium salt electrolyte composition of raw materials comprises 0.085-0.28mol/L NH
4H
2PO
4With 0.082-0.15mol/L Ca (CH
3COO)
2H
2O; Said phosphate electrolyte composition of raw materials comprises 15-16g/L Na
5P
3O
10, 1.5-2g/L NaOH, 0.5-1g/L Na
2WO
4And 1.7-1.9g/LNa
2EDTA.
The bionical deposition of drug molecule of urging endothelial growth or thrombolytic-anticoagulant on the described micropore ceramics oxidation film layer comprises the steps:
A, preparation pH are 4, and Ca and P mol ratio are 1.67 Ca (NO
3)
2(NH
4)
2HPO
4Mixed solution, and the drug molecule that can urge endothelial growth or thrombolytic-anticoagulant is dissolved in the solution, makes its mass concentration be mixed with 0.08-10%, carries out then sonic oscillation 15-20 minute, ultrasonic frequency is 30-50kHz;
B, treat the magnesium alloy bracket drying after, magnesium alloy bracket is put in the mixed solution that step a handles, temperature adjusting is in 60-100 ℃; Keep 30-60 minute ultrasonic periodic swinging; Wherein each sonic oscillation 5-15 minute, stopped supersound process 5 minutes, ultrasonic frequency is 50-60kHz; Make drug molecule be adsorbed on the nano hydroxyl phosphorite crystal surface of generation;
C, taking-up magnesium alloy bracket are put in the vacuum drying oven, and after dry 15-30 minute, deposited coatings thickness is 5-10 μ m between 40-120 ℃, and the rack surface coating of generation is smooth evenly.
The medicine of described short endothelial growth or thrombolytic-anticoagulant is one or more in short ECGF, antibiotic, anticoagulant molecule, solution fibrin drug molecule, anti-inflammation drugs molecule, paclitaxel, the non-steroidal drug molecule.Short ECGF in the rack surface preparation is in order to impel the outermost monofilm endotheliocyte of blood vessel wall rete to move in the rack surface growth effectively apace; Cover the probability that support contacts with blood with the minimizing support, thereby reduce the deposition probability of blood embolus at rack surface; The antibiotic medicine coating then is in order to suppress the growth migration of smooth muscle cell on rack surface, can stop the continuous hypertrophy of layer of smooth muscle cells of rack surface and forms restenosis; The effect of anticoagulant molecule and solution fibrin drug molecule coating all is to dissolve the blood embolus that contacts with support and avoid it constantly to deposit at rack surface; The blood vessel foreign body that anti-inflammation drugs can be prevented and treated in some support implantation process repels side effect; Paclitaxel combines with the tumor cell tubulin; Promote microtubule polymerization, suppress microtubule depolymerization, the blocking-up mitosis; Thereby inhibition tumor growth; Though have antitumaous effect comparatively, paclitaxel also has toxicity to existing atrioventricular conduction defect or diastolic dysfunction cardiovascular system, and the paclitaxel coating of support must especially could be used the cardiovascular tumour patient by practical situation in an amount of design; On-steroidal AID (NSAID) is one type of medicine with analgesic, pain relieving, antiinflammatory and the effect of inhibition platelet aggregation; The inactive suddenly aspirin antibiotic medicine of cardiovascular patient can increase recent cardiovascular event risk; Therefore need prepare the slowly nonsteroidal and-inflammatory drug coating of slow release at rack surface, can reduce the probability that the cardiovascular diseases sends out in the time of to blood anticoagulant.
Differential arc oxidation is a kind of new technique at non-ferrous metal surface in situ growth ceramic layer; It has strong with the metallic matrix adhesion, electrical insulating property good, excellent optical performance, heat shock resistance, characteristic such as wear-resistant, corrosion-resistant, the surfacecti proteon effect is far superior to the conventional surface processing method.In the magnesium alloy differential arc oxidation process, the electric energy part that power supply provides consumes in electrolyte, and the temperature of electrolyte is raise; Another part is used to generate ceramic membrane.In film forming procedure; The breakdown arc light that sends of gas; Because the instantaneous temperature of discharge microcell can be up to 2000 ℃; Strong reaction takes place in elemental gas and Mg alloy surface element under the high arc temperature effect, the oxide of molten state magnesium and other alloying element combines with the metallurgical binding mode under " liquid is quenched " cooling of electrolyte.The magnesium alloy differential arc oxidation film layer surface distributed of phosphate electrolyte system preparation a large amount of micropores of discharge uniformly, and the aperture is between 1-3 μ m, and porosity is the 2-50% that the total size of micropore accounts for the rete gross area.
The magnesium alloy blood vessel inner bracket for preparing molding as sample, after the ultrasonic surface purified treatment, is put into the electrolysis bath differential arc oxidation and handled.Mao power source is a high frequency switch power.Rustless steel is a negative electrode, and sample is an anode.With in deionized water preparation calcium salt electrolyte and the phosphate electrolyte, carry out differential arc oxidation, the micropore ceramics oxidation film layer that finally form thickness 10-100 μ m, has the 20-40% porosity respectively.
Bionical sedimentation is that a kind of of development in recent years deposits ionic a kind of biomaterial coating film covering method on the material matrix surface naturally in the solution that is similar to the human body environmental condition; It has more superiority in other biological coating processes such as plasma spraying, laser melting coating, SOL-GEL method, electrochemical depositions: carry out at low temperatures, for the codeposition protein and other provides probability; Can on complex-shaped and porous matrix, form coating uniform, that combine closely; Technology is simple, expense is lower.
The present invention has following advantage and beneficial effect with respect to prior art:
1, the present invention carries out the design of two layers of surface modified coating at present domestic and international up-to-date magnesium alloy blood vessel inner bracket; Can control the degradation rate of magnesium alloy in human vas effectively; It is more slow to compare with the degradation rate of domestic and international magnesium alloy blood vessel inner bracket (like Chinese invention patent application 20710012808.1), and the volume lifetime that the present invention has improved magnesium alloy blood vessel inner bracket has guaranteed that its mechanics supports the effect of dredging vascellum.
2, the present invention has used surface treatment method of Mg alloy-differential arc oxidation on magnesium alloy blood vessel inner bracket, can form the ceramic coating layer of one deck micropore shape at rack surface, makes the support matrix can avoid with contacting of blood degraded fast; The secondary high frequency micro-arc oxidation process that the present invention uses also can effectively be controlled the micropore porosity and the thicknesses of layers of rack surface ceramic coating layer, and through the degradation speed of these two parameter regulation and control supports, porosity is big more, and rete is thin more, and the scaffold degradation rate is fast more; The micropore shape of rack surface ceramic coating layer can more effectively closely deposit and the drug loading molecule, and can absorb the energy of flow of a part of rack surface blood flow.
3, the bionical depositing operation of drug molecule of the present invention's use, drug molecule is accompanied by the generation of nano hydroxyl phosphorite crystal and is adsorbed on plane of crystal in the mixed solution that is similar to the human body environmental condition; The ceramic coating layer that nano hydroxyl phosphorite crystal and rack surface differential arc oxidation generate has good deposition binding ability; Thereby at rack surface, play anticoagulation, thrombus dissolving, press down tumor, short endothelialization etc. prevents the effect of vascular restenosis the drug molecule close plating.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described, but the scope of protection of present invention is not limited to the scope that embodiment representes.
Embodiment 1:
Adopting quality purity is that 99.99% magnesium metal (all the other 0.01% be metallic aluminium) makes the blanketing with inert gas laser engraving be made into netted tubular stent sample, average twine footpath 0.1 ± 0.02mm, ultrasonic cleaning 10 minutes in acetone, ethanol respectively;
After support takes out drying, at output power of high-frequency switching power supply 400W, power density 160W/cm
2, under the switching frequency 200kHz condition, successively at 45 ℃ calcium salt electrolyte (0.28mol/L NH
4H
2PO
4, 0.082mol/LCa (CH
3COO)
2H
2O) and 50 ℃ phosphate electrolyte (15g/L Na
5P
3O
10, 1.6g/L NaOH, 1g/LNa
2WO
4, 1.85g/L two ethylenediamine hydrate tetraacethyl disodium (Na
2-EDTA)) differential arc oxidation that carries out 20 minutes and 15 minutes respectively handles, and makes the micropore ceramics oxidation film layer that rack surface obtains 75 μ m, has 40% porosity;
Preparation pH is 4, and Ca and P mol ratio are 1.67 Ca (NO
3)
2(NH
4)
2HPO
4In the mixed solution, and the short endothelial cell growth factor VEGF of molecular weight 3445kD is dissolved in the solution, makes its mass concentration be mixed with 4%, carried out sonic oscillation then 15 minutes, ultrasonic frequency is 50kHz.
After treating the support drying, support is put in mixed solution, temperature adjusting keeps 45 minutes ultrasonic periodic swinging in 60 ℃, and wherein each sonic oscillation 10 minutes stopped supersound process 5 minutes, and ultrasonic frequency is 50kHz.Make drug molecule be adsorbed on the nano hydroxyl phosphorite crystal surface of generation, crystal size is deposited in the surface micropore of support and fills and leads up smooth surface between 35nm simultaneously;
At last, take out support, be put in the vacuum drying oven, after dry 20 minutes, deposited coatings thickness is 5 μ m between 80 ℃, and the rack surface coating of generation is smooth evenly, and gross thickness is 80 μ m.
Magnesium endovascular stent after the surface modification is carried out artificial blood plasma degradation experiment, can observe obtaining after 400 days the magnesium endovascular stent and degrading fully.
Compare with 20710012808.1 disclosed 30 days drug release cycles of Chinese invention patent application and 0.5-5mm/year degradation rate; The magnesium endovascular stent thickness of present embodiment is 0.1 ± 0.02mm; 400 days complete degradation rate is about 0.09mm/year; Be that the vivo degradation rate of magnesium bracket obtains the present embodiment surface modified coat and effectively slows down control, support blood vessel is in vivo put and is deposited the time more of a specified duration, can fulfil the function of dredging vascellum.
Embodiment 2:
Adopt the AZ31 magnesium alloy to be made into the support sample, average silk footpath 0.1 ± 0.02mm, ultrasonic cleaning 12 minutes in acetone, ethanol respectively;
After support takes out drying, at output power of high-frequency switching power supply 380W, power density 200W/cm
2, under the switch lock 180kHz condition, successively at 50 ℃ calcium salt electrolyte (0.085mol/L NH
4H
2PO
4, 0.106mol/LCa (CH
3COO)
2H
2O) and 55 ℃ phosphate electrolyte (15.3g/LNa
5P
3O
10, 1.5g/LNaOH, 0.8g/LNa
2WO
4, 1.7g/L two ethylenediamine hydrate tetraacethyl disodium (Na
2-EDTA)) differential arc oxidation that carries out 25 minutes and 18 minutes respectively handles, and makes the micropore ceramics oxidation film layer that rack surface obtains 100 μ m, has 30% porosity;
Preparation pH is 4, and Ca and P mol ratio are 1.67 Ca (NO
3)
2(NH
4)
2HPO
4In the mixed solution, and the anticoagulant Low molecular heparin of cancer therapy drug polylactic acid and molecular weight 4kD is dissolved in the solution, makes its mass concentration be mixed with 10% and 0.08% respectively, carried out sonic oscillation then 20 minutes, ultrasonic frequency is 30kHz.Low molecular heparin can be replaced by anticoagulant molecules such as rapamycin and thrombin inhibitors.
After treating the support drying, support is put in mixed solution, temperature adjusting keeps 60 minutes ultrasonic periodic swinging in 80 ℃, and each sonic oscillation 15 minutes stopped supersound process 5 minutes, and ultrasonic frequency is 60kHz; Make drug molecule be adsorbed on the nano hydroxyl phosphorite crystal surface of generation, crystal size is deposited in the surface micropore of support and fills and leads up smooth surface between 35nm simultaneously;
At last, take out support, be put in the vacuum drying oven, after dry 15 minutes, deposited coatings thickness is 8 μ m between 120 ℃, and the rack surface coating of generation is smooth evenly, and gross thickness is 108 μ m.
To show that the magnesium endovascular stent after the modification carries out artificial blood plasma degradation experiment, and can observe obtaining after 460 days the magnesium endovascular stent and degrading fully.
Compare with 20710012808.1 disclosed 30 days drug release cycles of Chinese invention patent application and 0.5-5mm/year degradation rate; The magnesium endovascular stent thickness of present embodiment is 0.1 ± 0.02mm; 460 days complete degradation rate is about 0.08mm/year; Be that the vivo degradation rate of magnesium bracket obtains the present embodiment surface modified coat and effectively slows down control, support blood vessel is in vivo put and is deposited the time more of a specified duration, can fulfil the function of dredging vascellum.
Embodiment 3:
Adopt the AZ91 magnesium alloy to be made into support sample (average silk footpath 0.1 ± 0.02mm), ultrasonic cleaning 10 minutes in acetone, ethanol respectively;
After support takes out drying, at output power of high-frequency switching power supply 350W, power density 180W/cm
2, under the switch lock 250kHz condition, successively at 60 ℃ calcium salt electrolyte (0.217mol/L NH
4H
2PO
4, 0.15mol/LCa (CH
3COO)
2H
2O) and 60 ℃ phosphate electrolyte (16g/L Na
5P
3O
10, 2g/L NaOH, 0.5g/LNa
2WO
4, 1.9g/L two ethylenediamine hydrate tetraacethyl disodium (Na
2-EDTA)) differential arc oxidation that carries out 30 minutes and 20 minutes respectively handles, and makes the micropore ceramics oxidation film layer that rack surface obtains 110 μ m, has 20% porosity;
Preparation pH is 4, and Ca and P mol ratio are 1.67 Ca (NO
3)
2(NH
4)
2HPO
4In the mixed solution, and paclitaxel is dissolved in the solution, makes its mass concentration be mixed with 3%, carried out sonic oscillation then 18 minutes, 40kHz.
After treating the support drying, support is put in mixed solution, temperature adjusting keeps 30 minutes ultrasonic periodic swinging in 100 ℃, and each sonic oscillation 5 minutes stopped supersound process 5 minutes, and ultrasonic frequency is 50kHz; Make drug molecule be adsorbed on the nano hydroxyl phosphorite crystal surface of generation, crystal size is deposited in the surface micropore of support and fills and leads up smooth surface between 35nm simultaneously;
At last, take out support, be put in the vacuum drying oven, after dry 30 minutes, deposited coatings thickness is 10 μ m between 40 ℃, and the rack surface coating of generation is smooth evenly, and gross thickness is 120 μ m.
To show that the magnesium endovascular stent after the modification carries out artificial blood plasma degradation experiment, and can observe obtaining after 600 days the magnesium endovascular stent and degrading fully.
Compare with 20710012808.1 disclosed 30 days drug release cycles of Chinese invention patent application and 0.5-5mm/year degradation rate; The magnesium endovascular stent thickness of present embodiment is 0.1 ± 0.02mm; 600 days complete degradation rate is about 0.06mm/year; Be that the vivo degradation rate of magnesium bracket obtains the present embodiment surface modified coat and effectively slows down control, support blood vessel is in vivo put and is deposited the time more of a specified duration, can fulfil the function of dredging vascellum.
Claims (3)
1. method of modifying that is used for surface of magnesium alloy stent; The modification processing of surface of magnesium alloy stent differential arc oxidation and the bionical deposition of drug molecule that comprise controlled degradation; It is characterized in that: the magnesium alloy blood vessel inner bracket matrix surface carries out the magnesium alloy differential arc oxidation modification earlier to be handled; Form micropore ceramics oxidation film layer controlled degradation, that have fine and close porosity, thicknesses of layers 80-120 μ m, porosity 20-40%; On the micropore ceramics oxidation film layer, carry out urging the bionical deposition of drug molecule of endothelial growth or thrombolytic-anticoagulant, deposit thickness is 5-10 μ m;
It is after magnesium alloy bracket is taken out drying, to be 350-400W at output power of high-frequency switching power supply that described magnesium alloy differential arc oxidation modification is handled, and power density is 160-200W/cm
2, switching frequency is under the 180-250kHz condition, successively the phosphate electrolyte of 45-60 ℃ calcium salt electrolyte and 50-60 ℃ carry out respectively 20-30 minute with 15-20 minute differential arc oxidation, make rack surface obtain the micropore ceramics oxidation film layer; Said calcium salt electrolyte composition of raw materials comprises 0.085-0.28mol/L NH
4H
2PO
4With 0.082-0.15mol/L Ca (CH
3COO)
2H
2O; Said phosphate electrolyte composition of raw materials comprises 15-16g/L Na
5P
3O
10, 1.5-2g/L NaOH, 0.5-1g/L Na
2WO
4And 1.7-1.9g/LNa
2EDTA.
2. the method for modifying that is used for surface of magnesium alloy stent according to claim 1 is characterized in that, the bionical deposition of drug molecule of urging endothelial growth or thrombolytic-anticoagulant on the described micropore ceramics oxidation film layer comprises the steps:
A, preparation pH are 4, and Ca and P mol ratio are 1.67 Ca (NO
3)
2(NH
4)
2HPO
4Mixed solution, and the drug molecule that can urge endothelial growth or thrombolytic-anticoagulant is dissolved in the solution, makes its mass concentration be mixed with 0.08-10%, carries out then sonic oscillation 15-20 minute, ultrasonic frequency is 30-50kHz;
B, treat the magnesium alloy bracket drying after, magnesium alloy bracket is put in the mixed solution that step a handles, temperature adjusting is in 60-100 ℃; Keep 30-60 minute ultrasonic periodic swinging; Wherein each sonic oscillation 5-15 minute, stopped supersound process 5 minutes, ultrasonic frequency is 50-60kHz; Make drug molecule be adsorbed on the nano hydroxyl phosphorite crystal surface of generation;
C, taking-up magnesium alloy bracket are put in the vacuum drying oven, and after dry 15-30 minute, deposited coatings thickness is 5-10 μ m between 40-120 ℃, and the rack surface coating of generation is smooth evenly.
3. the method for modifying that is used for surface of magnesium alloy stent according to claim 1 is characterized in that: the medicine of described short endothelial growth or thrombolytic-anticoagulant is one or more in short ECGF, anticoagulant molecule and the solution fibrin drug molecule.
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Cited By (2)
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| US8986369B2 (en) | 2010-12-01 | 2015-03-24 | Zorion Medical, Inc. | Magnesium-based absorbable implants |
| CN114703530A (en) * | 2022-04-28 | 2022-07-05 | 徐州工程学院 | Method for compositely constructing samarium-doped hydroxyapatite gradient coating on surface of magnesium alloy by utilizing electrophoresis/micro-arc oxidation technology |
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| CN102552993B (en) * | 2011-11-15 | 2014-02-12 | 东南大学 | Magnesium alloy sheet-reinforced absorbable intrabony fixing composite material and preparation method thereof |
| CN103372232B (en) * | 2012-04-27 | 2015-06-10 | 中国科学院金属研究所 | Micro-arc oxidation self-sealing hole active coating of magnesium-based implant material and preparation method of micro-arc oxidation self-sealing hole active coating |
| CN103705294B (en) * | 2012-09-28 | 2016-03-02 | 上海微创骨科医疗科技有限公司 | Coating sustained-released system of multi-functional combination drug and preparation method thereof |
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